Monoazo compounds

ABSTRACT

An azo dyestuff of the formula:   WHEREIN R1&#39;&#39; and R2&#39;&#39; are each hydrogen, C1-C4-alkyl optionally interrupted by an oxygen atom and optionally substituted by phenyl, cyano, chlorine, bromine, fluorine, C1-C4-alkoxy, formylamino, formyloxy, C1-C5-alkylcarbonylamino, C1-C5alkylcarbonyloxy, benzoyloxy, benzoylamino, C1-C4alkylcarbamyloxy, phenylcarbamyl, C1-C4-alkyloxycarbonyloxy, phenoxycarbonyloxy, and phenoxy. Ring A may be optionally substituted with alkyl, alkoxy, aryl, aryloxy, arylthio, halogen, trifuloromethyl or acylamino groups. Of particular value are dyestuffs where ring A is not further substituted, X is NR, and one of R1&#39;&#39; and R2&#39;&#39; is cyanoethyl. The dyestuffs give fast dyeings of polyester textile material in shades of red and yellow.

United States Patent [191 Desai et al.

[ MONOAZO COMPOUNDS [73] Assignee: Ciba-Geigy AG, Basel, Switzerland[22] Filed: Dec. 15, 1971 [21] Appl. No.: 208,418

Related US. Application Data [63] Continuation-impart of Ser. No.806,291, March 11,

1969, Pat. No. 3,679,657.

[30] Foreign Application Priority Data Apr. 18, 1968 Switzerland 3958/68[52] US. Cl. 260/207.l, 260/207 [51] Int. Cl. C091) 29/08, C09b 29/26[58] Field of Search 260/207, 207.1

[56] References Cited UNITED STATES PATENTS l/l960. Jirou et al 260/207X 12/1970 Gunther et al 260/207 X Dec. 10, 1974 3,598,803 8/1971 Henrardet al 260/207 X Primary Examiner-Lorraine A. Weinberger AssistantExaminerC. F. Warren Attorney, Agent, or Firm-Joseph G. Kolodny; EdwardMcC. Roberts; Prabodh I. Almaula [57] ABSTRACT An azo dyestuff of theformula:

wherein R and R are each hydrogen, C C -alkyl optionally interrupted byan oxygen atom and optionally substituted by phenyl, cyano, chlorine,bromine, fluorine, C,-C -alkoxy, formylamino, formyloxy, c c-alkylcarbonylamino, C C -alkylcarbonyloxy, benzoyloxy, benzoylamino, CC.,-alkylcarbamyl0xy, phenylcarbamyl, C C -alkyloxycarbonyloxy,phenoxycarbonyloxy, and phenoxy. Ring A may be optionally substitutedwith ,alkyl, alkoxy, aryl, aryloxy, arylthio, halogen, trifuloromethylor acylamino groups. Of particular value are dyestuffs where ring A isnot further substituted, X is NR, and one of R and R is cyanoethyl. Thedyestuffs give fast dyeings of polyester textile material in shades ofred and yellow.

2 Claims, No Drawings (4'-chloro)-phenylthiazole,

MONOAZO COMPOUNDS This Application is a Continuation-in-Part of US.application Ser. No. 806,291, filed Mar. 1 1, 1969, which issued as US.Pat. No. 3,679,657 on July 25, 1972..

The present invention relates to new valuable compounds possessingdyestuff character, which contain at least one group of formula XCONRSOwherein R is an acyl group or preferably a hydrogen atom or anoptionally substituted alkyl, cycloalkyl, aryl or heterocyclic group,and X is an oxygen or sulphur atom or a group of formula NR wherein R isan acyl group or preferably a hydrogen atom or an optionally substitutedalkyl, cycloalkyl, aryl or heterocyclic group The groups R and R caneach for example be methyl, ethyl, propyl or benzyl groups.

The invention for example relates to azo dyestuffs, especially monoazodyestuffs and disazo dyestuffs, anthraquinones, perinones,quinphthalones, styryl dyestuffs and nitro dyestuffs.

AZO DYESTUFF S The particularly interesting dyestuffs include themonoazo dyestuffs of formula DN=NA NR R wherein D is the residue of adiazo component, A is an arylene residue, especially an optionallysubstituted 1,4phenylene residue, R and R are each an optionallysubstituted alkyl group, with at least one of the residues D, A, R, andR containing a group of formula XCONR--SO .R wherein R is a monovalentresidue, especially an aliphatic, a cycloaliphatic, araliphatic,aromatic or heterocyclic residue, such as for example a methyl, ethyl,n-propyl, n-butyl, cyclohexyl, p-tolyl, 2,5-dimethylphenyl, 4-( chloro,fluoro or bromo) phenyl, benzthiazole-2, pyridyl or thienyl-2 residue.

The diazo residue D is mainly derived from monocyclic or bicyclic aminesof formula D-NH such as any desired diazotisable heterocyclic amineswhich do not contain any acid substituents conferring solubility inwater, but especially from amines which possess a heterocyclicfive-membered ring with 2 or 3 hetero-atoms, above all a nitrogen atomand one or two sulphur, oxygen or nitrogen atoms as hetero-atoms, andaminobenzenes, especially those of formula wherein a denotes a hydrogenor halogen atom, or an alkyl or alkoxy, nitro, nitrile, carbalkoxyoralkylsulphone group, b denotes a hydrogen or halogen atom, or an alkyl,nitrile or trifluoromethyl group, denotes a nitro, nitrile, carbalkoxy,aryl or alkylsulphonyl group and d denotes a hydrogen atom, a halogenatom, a carboxylic acid ester group or a carboxylic acid amide group.

The following may be mentioned as examples: 2- aminothiazole,2-amino-5-nitrothiazole, 2-amino-5- methylsulphonylthiazole,2-amino-5-cyanothiazole, 2- amino-4-methyl-5-nitrothiazole, 2-amino-4-methylthiazole, 2-amino4-phenylthiazole, 2-amino-4-2-amino-4-(4'-nitro)- phenylthiazole, 3-aminopyridine, 3-aminoquinoline,

3-aminopyrazole, 3-aminol -phenylpyrazole, 3- aminoindazole,3-amino-l,2,4-triazole, S-(methyl, ethyl, phenyl orbenzyl)-l,2,4-triazole, 3-amino-l-(4- methoxyphenyl)-pyrazole,2-amino-benzthiazole,

2-amino--methylbenzthiazole, 2-amino-6- methoxybenzthiazole,2-amino-6-chlorobenzthiazole, 2-amino-6-cycanobenzthiazole, 2-amino-6-dichlorobenzene, l-amino-2,5-dichlorobenzene 1-amino-2,4-dibromobenzene,l-amino-2-methyl-4- chlorobenzene, l-amino-2-trifluoromethyl-4-chlorobenzene, l-amino-2-cyano-4-chlorobenzene, 1-amino-2-carbomethoxy-4-chlorobenzene, 1-amino-2-carbomethoxy-4-nitrobenzene, 1-amino-2-chloro-4- cyanobenzene,l-amino-2-chloro-4-nitrobenzene, 1- amino-2-bromo-4-nitrobenzene,l-amino-2-chloro-4- carbethoxybenzene,1-amino-2-chloro-4-methylsulphonylbenzene, 1-amino-2-methysulphonyl-4-chlorobenzene, l-amino-2-methylsulphonyl-4-nitrobenzene,l-amino-2,4-dinitrobenzene, l'-amino2,4- dicyanobenzene,1-amino-2-cyano-4-methylsulphonylbenzene,1-amino-2,6-dichloro-4-cyanobenzene, 1-amino-2,6-dichloro-4-nitrobenzene, l-amino-2,4-

dicyano-6-chlorobenzene, 4-aminobenzoic acid cyclov hexyl ester,l-amino-2,4-dinitro-6-chlorobenzene and especiallyl-amino-2,-cyano-4-nitrobenzene, and also l-aminobenzene-2-, -3- or-4-sulphonic acid amides, such as the N-methylamide orN,N-dimethylamideor N,N-diethylamide.

Diazo components of formula wherein a, b or 0' denote a residue offormula X-N- R-SO -R should be mentioned particularly.

The group A is preferably the residue of formula wherein c and d arehydrogen atoms or methyl, ethyl, methoxy, ethoxy, phenylthio or phenoxyresidues.

The group 0 is preferably bonded in the orthoposition to the azo groupand can, in addition to the above-mentioned groups, also denote achlorine or bromine atom, a trifluoromethyl group, an alkylsulphonylgroup, preferably a methylsulphonyl group, and an acylamino group whichis optionally alkylated, preferably methylated, at the nitrogen atom andin which the acyl residue is the residue of an organic monocarboxylicacid, an organic monosulphonic acid, such as methanemonosulphonic,ethanemonosulphonic or p toluenemonosulphonic acid, or the residue of acarbamic acid monoester or monoamide or of a carbonic acid monoester ormonoamide, such as phenoxycarbonyl, methoxycarbonyl and aminocarbonyl.or the residue of formula CONRSO R The groups R, and R may be hydrogenatoms or lower alkyl groups, that is to say alkyl groups containing 1 to4, preferably 2 to 4, carbon atoms, such as methyl, ethyl, n-propyl orn-butyl groups which may be substituted in the usual manner such as forexample benzyl or B-phenylethyl groups, halogenated alkyl groups, suchas B-chlorethyl, B,B,B-trifluorethyl, ,8, y-dichloropropyl,fi-cyanethyl, alkoxyalkyl, such as B-ethoxyethyl or 8 -methoxybutyl,hydroxyalkyl, such as B-hydroxyethyl, B, y-dihydroxypropyl, nitroalkyl,such as B-nitroethyl, carbalkoxy, such as B-carbo- (methoxy, ethoxy orpropoxy)-ethyl (with the terminal alkyl group being permitted to carrynitrile, carbalkoxy, acyloxy and amino groups in the to position), ,8-or y-carbo-(methoxy or ethoxy)-propyl, acylaminoalkyl, such as B-(acetylor formyl)-aminoethyl, acyloxyalkyl, such as B-acetoxyethyl,B,'y-diacetoxypropyl, B-(alkyl or aryl)-sulphonylalkyl, such asB-methanesulphonylethyl, B-ethanesulphonylethyl orB-(pchlorobenzenesulphonyl)-ethyl, alkylor arylcarbamoyloxyalkyl, suchas B-methylcarbamyloxyethyl and B-phenylcarbamyloxyethyl,

alkyloxycarbonyloxyalkyl, such as B-(methoxy, ethoxy orisopropoxy)-carbonyloxyethyl, 'y-acetamidopropyl, B-(p-nitrophenoxy)-ethyl, B-( p-hydroxyphe noxy ethyl, B-(,8-acetylethoxycarbonyl)-ethyl,B-[B'cyano, hydroxy, methoxy or acetoxy)ethoxycarbonyll-ethyl,cyanalkoxyalkyl, B-carboxyethyl, B-acetylethyl, y-aminopropyl,B-diethylaminoethyl, B-cyanacetoxyethyl and B-benzoyl-B-(p-alkoxy orphenoxybenzoyl )-oxyethyl groups.

Particularly preferably, R and/or R denote a residue of formulaalkyleneXCO-NRSO -R such as for example a B-(N-phenylsulphonyl-N-methylaminocarbonyloxy)-ethyl or a y-(N-methylsulphonyl-N-methylaminocarbonylamino)- propyl residue.

The groups R, and R generally contain not more than 18 carbon atoms.

Another preferred type of monoazo dyestuffs has the formula R SONRCOXD'N=NA', wherein D is an optionally substituted p-phenylene residueand A is the residue of a coupling component such as for example aphenol, an enol, an aromatic amine or u pyrazolone, D preferably being aresidue of formula wherein a and b have the same significance as above.

Particularly preferred disazo dyestuffs are those of formula wherein D,A, R, R" and X have the same significance as above and R is a bivalentorganic residue, especially an aliphatic, araliphatic, cycloaliphatic,aromatic or heterocyclic residue such as for example ahexarnethylene-l,6- or phenylenel ,3 residue.

Further dyestuffs to be mentioned are the tlisazo dyestuffs of formulawherein R and R 40 have the same significance as above, and the disazodyestuffs of formula N=N-A wherein R, R R D and A have the samesignificance as above and D is a p-phenylene residue.

STYRYL DY ESTUFFS Preferred styryl dyestuffs are those of formulawherein A, R, and R have the same significance as above and Y is anitrile, carbalkoxy or arylsulphonyl group, such as for example acarbethoxy or phenylsulphonyl group.

Particularly interesting dyestuffs are those of formula wherein R is analkyl group or preferably an aromatic group such as a phenyl group and Ris an alkyl, or aralkyl group or the residue of formula CH C- H OCON(CH)SO R Preferred bis-styryl dyestuffs are those of formula wherein R, R RA, X and Y have the same significance as above.

ANTHRAQUINOID DYESTUFFS heterocyclic residues, arylamino groups, whereinthe aryl residue is preferably a phenyl group which may be substitutedby one or more halogen atoms, alkyl or alkoxy groups, alkylsulphonyl oroptionally substituted phenylsulphonyl groups, alkylthioether oroptionally substituted phenylthioether residues as well as nitro,nitrile, carboxylic acid ester and acetyl groups. Examples oftetracyclic anthraquinone residues are 1,9- isothiazolanthrone,1,9-anthrapyrimidine or 1,9- pyrazolanthrone. The alkyl residues arepreferably lower alkyl residues which can contain up to 6 carbon atoms.

Preferred anthraquinone dyestuffs are for example those of formula l n-iwherein B denotes a halogen atom, especially a bromine or chlorine atom,or an alkyl or alkoxy group, especially methyl or methoxy, n l or 2 andZ Z Z and Z each denote a hydrogen atom, an amino or hydroxyl groupwhich is optionally substituted by an alkyl, aralkyl, cycloalkyl, arylor heterocyclic residue, or an amino or hydroxyl group substituted by anorganic acid residue, with at least one of the symbols Z Z 2;, or 2.,containing or denoting a group of formula X- CO-NRSO R such as forexample a group of formula NHC H NHCONHSO R or N(CH )CON(CH )SO -Rwherein R has the same significance as given above.

Other preferred anthraquinone dyestuffs are for example those of formulawherein Z Z Z 2,, B, n, X, R and R have the same significance as above,A" is an aliphatic, araliphatic, aromatic or heterocyclic residue whichis optionally interrupted or substituted by hetero-atoms, and X is adirect bond, 21 sulphonyl, sulphonyloxy or sulphonylamino group or hasthe same significance as given forX. Amongst these dyestuffs, thesubgroup wherein the symbol X is a direct bond. the symbol Hal is achlorine or'bromine atom, the group X is an oxygen atom and the group Ris a lower alkyl residue or .a hydrogen atom, and the group A" is ap-phenylenc residue which can furthermore carry alkoxy. hydroxyl,

phenoxy or acyloxy groups is particularly of interest.

The new dyestuffs are manufactured (a) by reacting a dyestuff whichcontains at least one group of formula XH, wherein X has the samesignificance as above, with at least one sulphonylisocyanate whichcontains at least one group of formula -SO -N=C=O or (b) by linking twocomponents of which at least one component contains at least one groupof formula X- -CONRSO by condensation or coupling to give a dyestuffwhich contains at least one group of formula XCONRSO or (c) by acylationor preferably NC condensation (with the formation of a N-C bond) of acompound possessing dyestuff character which contains at least one ofthe groups of formulae -XCO NHSO or NHCONR- SO with a compound which ispreferably an alkylating compound.

Stage (c) serves to introduce the groups R and/or R,.

I. PROCESS VARIANT (a) A. Sulphonylisocyanates:

Possible sulphonylisocyanates for embodiment (a) are optionallysubstituted aliphatic, cycloaliphatic, araliphatic, aromatic andheterocyclic sulphonylisocyanates such as for examplemethylsulphonylisocyanate,

ethyl-sulphonylisocyanate, isopropyl-lsulphonylisocyanate,n-propyl-l-sulphonylisocyanate, n-butyl-l-sulphonylisocyanate,propen-l-ylsulphonylisocyanate, n-hexen-l-yl-sulphonylisocyanate,4,4-dichlorobuten-l-yl-sulphonylisocyanate, 2-chlorovinyl-sulphonylisocyanate, cyclohexyl-lsulphonylisocyanate,cyclohexen-l-ylsulphonylisocyanate, 2-chlorethylsulphonylisocyanate,2-chloropropylsulphonylisocyanate, 2-chlorohexylsulphonylisocyanate,2-methyl-2-chloropropylsulphonylisocyanate, 2-vinyl-sulphonylisocyanate,phenyl-sulphonylisocyanate, 4-toly-sulphonylisocyanate,4-chlorophenyl-sulphonylisocyanate, 4-fluorophenyland thesulphonyldiisocyanate of formula SO (NCO) The general manufacture of thesulphonylisocyanate is described by Henri Ulrich, Chemical Reviews,1965,

.pages 369-371 and by Henri Ulrich and A. A. R.

Sayigh, Zeitschrift fur angewandte Chemie, pages 761-769.

The sulphonylisocyanates are particularly conveniently manufactured byphosgenation of sulphonamides such as for example ofmethanesulphonamide, ethanesulphonamide, l-butanesulphonamide, 1,3-propanedisulphonamide, 1 -propanesulphonamide, ethylenemonosulphonamide,a-toluenesulphonamide,

phenethylsulphonamide, benzensulphonamide, otoluenesulphonamide,p-toluenesulphonamide pacetylamino-benzenesulphonamide, 4

1 cHgcmcN CHQCHQOH NHCO Clli Cgll 2. Anthraquinone dyestuffsl-aminoanthraquinone, Z-aminoanthraquinone,lamino'5-chloro-8-hydroxyanthraquinone, l-amino-Z- bromanthraquinone,l-amino-5-hydroxy-6,8- dichloranthraquinone, l-amino-S ,8-dichloranthraquinone, l-amino-5-nitroanthraquinone, l-amino-5-chIoro-8-me thoxyanthraquinone, l-amino- 7-chloranthraquinone,l-amino-6-chloranthraquinone,

CHzCHzOH 5. Perinone dyestuffs.

Mixtures of the dyestuffs of formula X X 1 I or mixtures of thedyestuffs of formula higher temperatures. Normally the solution of thesulphonylisocyanate is added slowly to the dyestuff which is to bereacted or to the dyestuff component which is to be reacted. The otherconditions for a selective reaction, such as low temperature, optionallybelow room temperature, and the use of dilute solutions of the reagents,are also observed. If necessary, reactive groups which are present suchas hydroxyl or amino groups are protected with suitable protectivegroups, for example acyl residues, optionally in the presence ofcatalysts,

for example pyridine.

ll. PROCESS VARIANT (b) A. Azo dyestuffs (coupling) The azo dyestuffsaccording to the invention can also be obtained by coupling a diazoniumcompound of an amine with a coupling component. with at least one of thecomponents having to contain a group of formula XCONRSO -R l. Diazocomponents:

Suitable diazo components which contain the group of formula XCONRSO Rare obtained by reaction of an aromatic or heterocyclic nitro compoundwhich possesses at least one group of formula XH, such as for example2-hydroxy-4-methylsulphonyl-nitrobenzene, 4-hydroxy-Z-methylsulphonylnitrobenzene or2,6-dichloro-4-hydroxy-nitrobenzene with a sulphonylisocyanate, anoptionally occurring alkylation of the imino group, and subsequentreduction of the nitro group.

As diazo components without groups of formula X- CONR-SO it is possibleto use the abovementioned diazo components of formula DNH to the extentthat these are not derived from a sulphonylisocyanate.

2. Coupling components Suitable coupling components which contain agroup of formula XCO-NRSO are obtained by reaction of one of thecomponents given below with a sulphonylisocyanate and optionaisubsequent alkylation: N-B-hydroxyethyl-N-ethylaniline,N-B-hydroxyethyl- N-cyanethylaniline, N,N-bis-B-hydroxyethylaniline, 3-acetamino--rnethoxy-N,N-bis-B-hydroxyethylaniline,3-amino-N,Nbisfifi-acetoxyethylaniline, 3-amino-N,N-bis-fl,B-cyanethylaniline, l-B-hydroxyethyl- 3-methylpyrazonlone-(S), and the B-hydroxyethylamide ofShydroxynaphthalene-S- or -6-sulphonic acid.

As coupling components without groups of formula XCONRSO the followingmay for example be mentioned: Nfi-cyanethylN-methylaminobenzene,N,N-di-B-hydroxyethylaminobenzene, l-N-B-cyanethyl-N-ethylamino-3-methylbenzene, 3- cyano-Z ,6-dihyd roxy-4-methyl pyridine lN-B-cyanethylamino-3-methylbenzene, l -N,N-di-B-hydroxyethyl-amino-3-thiocyanatobenzene, N-B- cyanethyl-naphthasultam-(l.8), l-N .N-di-B-cyanethyl-3-methyl-aminobenzene, N ,B-cyanethyl-N ,B-hydroxyethyl-aminobenzene, N,B-cyanethyl-2-methylindole,N,B-cyanethyl-tetrahydroquinoline, N-phenylaminobenzene, 4-hydroxyl-methylquinolone-( 2 l-hydroxy-4-meth ylbenzene, 2hydroxy-3-naphtholacid-o-anisidide. S-hydroxyquinoline, 2-naphthylamine-S-sulphomethylamide, 1,3- dihydroxybenzene,l-hydroxy-3-cyanomethylbenzene, l-phenyl-3-methyl-5-pyrazolone andacetoacetic ester.

3. Diazotisation and Coupling The diazotisation of the diazo componentsmentioned can take place according to methods which are in themselvesknown, for example with the aid of a mineral acid and sodium nitrite orfor example with a solution of nitrosylsulphuric acid in concentratedsulphuric acid.

The coupling can also be carried out in a manner which is in itselfknown, for example in a neutral to acid medium, optionally in thepresence of sodium acetate or similar buffer substances which influencethe coupling speed, or of catalysts such as for exampledimethylformanide, pyridine or their salts.

The coupling also takes place advantageously if the components arecombined by means of a mixing nozzle. This is to be understood as adevice in which the liquids to be mixed are combined with one another ina relatively small space. with at least one liquid being passed througha nozzle, preferably at an elevated pressure. The mixing nozzle can forexample be constructed, and can operate, according to the principle of awater-jet pump, with the feed of one liquid into the mixing nozzlecorresponding to the feed of water into the waterpump and the feed ofthe other liquid into the mixing nozzle corresponding to the connectionof the water-jet pump to the vessel which is to be evacuated, with thislatter liquid feed also being allowed to take place at elevatedpressure. Other suitable devices can however also serve for rapidoptionally continuous mixing in a small space.

After the coupling reaction has taken place the re sultingnon-quaternised dyestuffs can easily be separated from the couplingmixture, for example by filtration, since they are practically insolublein water. If the resulting dyestuffs are quatemised, they are saltedout.

B. Styryl dyestuffs (condensation) In order to manufacture the styryldyestuffs according to the invention, for example an aldehyde of formula, wherein c" represents a hydrogen atom or preferably a methyl group andR and R have the significance given above, can be condensed with anitrile compound formula with the application of heat in the presence ofa basic catalyst such as for example ammonia, dimethylamine,diethylamine, piperidine, piperidine acetate, sodium alcoholate orpotassium alcoholate, optionally in the presence of a solvent such asmethanol, ethanol, benzene, toluene, xylene, chloroform or carbontetrachloride. Suitable nitrile compounds of formula NC-CH- -X for thereaction of the styryl dyestuff are for example: malonic acid dinitrile,cyanacetic acid methyl ester, cyanacetic acid ethyl ester, cyanaceticacid butyl ester, cyanacetamide, cyanacetmethylamide,cyanacetdimethylamide, methylsulphonylacetonitrile andphylsulphonylacetonitrile.

When using solvents the water produced in the reaction can becontinuously removed from the reaction mixture by azeotropicdistillation of these solvents, as a result of which the reactionequilibrium is constantly displaced in favour of the condensationproduct. The condensation can also take place without a basic catalystin glacial acetic acid or some other organic acid or in the presence ofa solvent by fusing the reagents together in the presence of a basiccatalyst, for example ammonium acetate or piperidine acetate.

Anilines which are suitable as starting products are for exampleobtained by reacting a sulphonylisocyanate with for example3-methyl-N,N-bis-B-hydroxyeth yl-aniline,3-methyl-N-benzyl-N-Bhydroxyethylaniline,3-methyl-N-phenoxyethyLN-B-hydroxyethylaniline,3-methyl-N-B-acetoxyethyl-N-B-hydroxyethylaniline,3-methyl-N-ethyl-N-B-hydroxyethyl-aniline or7-methyl-N-B-hydroxyethyl-quinoline.

C. Nitro dyestuffs (condensation) In order to manufacture ditrodyestuffs, a sulphonylisocyanate of formula l NO:

(manufactured by phosgenation of the suplhonamide can be condensed with2 equivalents of an aniline which is optionally substituted at thearomatic nucleus.

The imino groups of the residues -OCON- HSO -NHCONHSO SCO--N- HSO NR-CONHSO and N- H-CONRSO is effected by adding alkylating agents such asfor example dimethylsulphate, diethylsulphate, methyl chloride, ethylbromide, methanesulphonic acid methyl ester or the methyl or ethylesters of 4-methyl-, 4-chloro-, or 4-nitro-benzenesulphonic acid insuitable organic solvents such as for example xylene, carbontetrachloride, o-dichloro-benzene, nitrobenzene, dimethylformamide,dimethylsulphoxide, acetonitrile or dioxane, optionally with warming.

Further Variants of the Manufacturing Process of SulphonyLUrethanesAccording to the Invention 1. Reaction chhorocarbonic acid esters withalkali salts of sulphonamides or with the free sulphonamides in thepresence of alkali carbonate, with at least one of the two organiccomponents having the posses dyestuff character.

2. Reaction of the alkali or alkaline earth salts of sulphonamides whichposses dyestuff character with pyrocarbonic acid esters in solution orin suspension up to temperatures of C and isolation of the freesulphonyl-urethanes from the resulting sulphonylurethane salts.

. 3. Decomposition of sulphonylureas with alcohols possessing dyestuffcharacter.

4. Reaction of sulphochlorides with urethanes, with the sulphochloridesand/or the urethanes possessing dyestufi character.

to the manufacture of the dyestuffs. Suitable quaternisable groups arefor example those of formulae and -CONH-NR NR wherein R and R are alkylresidues which together can form a chain which is optionally interruptedby hetero-atoms, and the group of formula as well as other heterocyclicstructures which can be quaternised to cyclammonium groups, such as forexample the residues of the abovementioned heterocyclic diazo componentsof formula D-Nl-l,

The quaternisation is effected by treatment with esters of strongmineral acids or organic sulphonic acids such as for exampledimethylsulphate, diethylsulphate, alkyl halides, such as methylchloride, methyl bromide or methyl iodide, aralkyl halides, such asbenzyl chloride, esters of low molecular alkanesulphonic acids, such asfor example the methyl ester of methanesulphonic, ethanesulphonic orbutane-sulphonic acid and the alkyl esters of (4-methyl-, 4-chloro-or 3-or 4-nitro-)benzenesulphonic acid, which form halogen, sulphuric acidhalf-ester, alkanesulphonic or benzenesulphonic acid anions as anions,preferably whilst warming in inert organic solvents, for example xylene,carbon tetrachloride, o-dichlorobenzene and nitrobenzone. It is howeveralso possible to use solvents such as acetic anhydride,dimethylformamide, acetonitrile or dimethylsulphoxide. The quaterniseddyestuffs preferably contain, as the anion Y, the residue of a strongacid such as sulphuric acid or its half-esters, or a halide ion, but canalso be used as double salts, for example with zinc chloride, or as freebases.

The quaternised dyestuffs for example correspond to the general formulaeCH3 ell asis...

wherein p is a hydrogen atom, a C C alkyl group or a negativesubstituent, and D, A, R' R' Z Z and 2., have the same significance asabove.

III. USE

The dyestuffs described above as a rule contain no acid groups whichconfer solubility in water, especially no sulphonic acid groups, and aretherefore sparingly soluble 0r insoluble in water. If they containquaterinised nitrogen atoms they are on the other hand soluble in water.

The water-insoluble dyestuffs, their mixtures with one another and theirmixtures with other azo dyestuffs are, especially after conversion to afinely divided form, for example by grinding, conversion to pastes,reprecipitation etc., excellently suited to the dyeing and printing ofsynthetic fibres such as for example acrylic or acrylonitrile fibres,polyacrylonitrile fibres and copolymers of acrylonitrile and other vinylcompounds such as acrylic esters, aerylamides, vinylpyridine, vinylchloride or vinylidene chloride, eopolymers of dicyanethylene and vinylacetate, as well as fibres of acrylonitrile block copolymers, fibres ofpolyurethanes, polyolefines, cellulose triacetate and Zia-acetate,polyamides, such as nylon 6, nylon 6,6 or nylon 12, and especiallyfibres of aromatic polyesters such as those obtained from therephthalicacid and ethylene glycol or l,4-dimethylolcyclohexane, and copolymers ofterephthalic and isophthalic acid and ethylene glycol.

The subject of the present invention is therefore also a process for thedyeing or printing of synthetic fibres, especially of polyester fibres,which is characterised in that dyestuffs which are free of carboxyl andsulphonic acid groups, which contain at least one group of formulaXCONRSO2, wherein R is an acyl group or preferably a hydrogen atom or anoptionally substituted alkyl, cycloalkyl, aryl or heterocyclic group andX is an oxygen or sulphur atom or a group of formula NR wherein Ry is anacyl group or preferably a hydrogen atom or an optionally substitutedalkyl, cycloalkyl, aryl or heterocyclic group. their mixtures with oneanother or their mixture with other dyestuffs are used.

Preferably, azo dyestuffs, especially monoazo dyestuffs and disazodyestuffs, anthraquinones, perinones, styryl dyestuffs and nitrodyestuffs are used.

Amongst the types of fibres, the group of fibres containing estergroups, and above all the polyester fibres, deserve particular emphasis.

For dyeing, the water-insoluble non-quaternised dyestuffs areappropriately used in a finely divided form and dyeing is effected withthe addition of dispersing agents such as sulphite cellulose waste lyeor synthetic detergents, or a combination of various wetting anddispersing agents. As a rule it is appropriate to convert the dyestuffsto be used, before dyeing, into a dyeing preparation which contains adispersing agent and finely divided dyestuff in such a form that ondilution of the dyestuff preparations with water a fine dispersion isproduced. Such dyestuff preparations can be obtained in a known manner,for example by grinding the dyestuff in a dry or wet form with orwithout the addition of dispersing agents during the grinding process.The above-mentioned synthetic fibres can also be dyed in organicsolvents in which the dyestuff is present as a solution.

In order to achieve intense dyeings on polyethylene terephthalate fibresit proves appropriate to add a swelling agent to the dyeing bath or tocarry out the dyeing process under pressure at temperatures above C, forexample at C. Suitable swelling agents are aromatic carboxylic acids,for example benzoic acid or salicylic acid, phenols such as for exampleo or p-hydroxydiphenyl, salicylic acid methyl ester, aromatic halogencompounds such as for example chlorobenzene, o-dichlorobenzene ortriehlorobenzene, phenylmethylcarbinol or diphenyl. When dyeing underpressure it proves advantageous to render the dyeing bath weakly acid,for example by adding a weak acid, for example acetic acid.

The non-quaternised water-insoluble dyestuffs to be used in accordancewith the invention prove to be particularly suitable for dyeingaccording to the so-called thermofixing process, according to which thefabric to be dyed is impregnated with an aqueous dispersion of thedyestuff which appropriately contains, 1 to 50 percent of urea and athickener, especially sodium alginate, preferably at temperatures of atmost 60C, and is squeezed out in the usual manner. It is appropriate tosqueeze out in such a way that the impregnated goods retain 50 to 100percent of their starting weight of dyeing liquor. 4 v l In order to fixthe dyestuff, the fabric impregnated in this way is, appropriately aftera prior drying, for example in a warm stream of air, heated totemperatures of above 100C, for example between 180 and 210C.

The thermofixing process which has just been mentioned is of particularinterest for dyeing mixed fabrics of polyester fibres and cellulosefibres; especially cotton. In this case the padding liquor contains, inaddition to the non-quaternised water-insoluble dyestuff .to-be usedaccording to the invention, also dyestuffs which are suitable for dyeingcotton, for example direct dyestuffs or vat dyestuffs, or especiallyso-called reactive dyestuffs, that is to say dyestuffs which can befixed to the cellulose fibre .with the formation of a chemical bond,that is to say for example dyestuffs containing a chlorotriazine orchlorodiazine residue. In the latter case it proves appropriate to addan acidbinding agent, for example an alkali carbonate or alkaliphosphate, alkali borate or alkali perborate or their mixtures to thepadding solution. When using vat dyestuffs it is necessary'for thepadded fabric after heat treatment to be treated with an aqueousalkaline solution of a reducing agent which is usual in vat dyeing.

The dyeings on'polyester fibresobtained' according to the presentprocess are appropriatelysubjected to a post-treatment,'for example'byheating with an aqueous solutionof'a non-ionicdetergentf Instead ofbeing applied by impregnation, the dyestuffs specified can, according tothe present process, also be applied by printing. For this purpose aprinting ink is for example used which in addition to the auxiliarysubstances usual in printing, such as wetting agents and thickeners,contain the finely dispersed dyestuff optionally mixed with one of theabove-mentiond cotton dyestuffs, optionally in the presence of ureaand/or an acid-binding reagent.

Using the present process, intense dyeings and prints of excellentfastness properties, especially good fastness to light, sublimation,decatising, washing and chlo.

rine water are obtained. The dyeings on acetate rayon are furthermoredistinguished by good gas fastness. A

further advantage resides in the good wool and cotton reserve of thedyestuffs to be used in accordance withthe process.

The new water-insoluble non-quaternised dyestuffs can also be used forthe spin dyeing of polyamides,

polyesters and polyolefines. The polymer to be dyed is.

appropriately mixed, in the form of powders, granules or chips, as afinished spinning solution or in the fused state, with the dyestuffwhich is introduced in the dry state or in the form of a dispersion orsolution in a SO]? vent which may be volatile. After homogeneousdistribution of the dyestuff in the solution or melt of the polymer themixture is'processed in a known manner by casting, pressing or extrusionto give fibres, yarns, monofilaments, films and the like.

The new water-soluble quaternised dyestuffs or dyestuff salts aresuitable for dyeing and printing the most diverse fully synthetic fibressuch as for example polyvinylchloride, polyamide, polyurethane andespecially polyacrylic fibres; j 1

The new dyestuffs are furthermore also suitable for the bulk colouringof polymerisation products of acrylonitrile, of polyolefines and also'ofother plastic compositions, and are also suitable for thecolouring ofoil paints and lacquers. It is also possible to use the abovementionedthermofixing process.-

The new water-insoluble non-quaternis'ed dyestuffs in part alsorepresent valuable pigments which can be used for the most diversepigment applications, for example in a finely divided form for dyeingrayon and viscose or cellulose ethers and esters, for the manufacture ofinks, especially' of ball pen inks, as well. as for the manufacture ofcoloured lacquers or lacquer-forming substances, solutions andproducts-made of acetylcellulose, nitrocellulose, natural resins orsynthetic resins, such as polymerisation resins or condensation resins,for example aminoplasts, alkyd resins, phenoplasts, polyolefines such aspolystyrene, polyvinyl chloride, polyethylene, polypropylene,polyacrylonitrile, rubber,

' casein, silicone and silicone resins.

The dyestuffs which are fully methylated at the sulphonyl-urea ormethane group are particularly suitable for dyeing polyolefine fibressuch as polypropylene fibres from an aqueous or organic liquor, aboveall the padding-thermo-fixing process.

' In the examples which follow the parts, unless otherwise specified,denote parts] by weight and the percent- NC caHs is filtered off, washedwith methanol and dried. it dyes polyester fibres from boilingtetrachlorethylene to give greenish-tinged yellow shades.

' EXAMPLE 2 4 parts .of 4-[N,N-bis-(2'-hydroxyethyl)-amino]-2-methyl-benzylidenemalodinitrile are dissolved in parts by volume of hotchlorobenzene and a solution of 6.6 parts ofp-toluenesulphonylisocyanate in l 00 parts by volume of chlorobenzene isadded dropwise. The

mixture is allowed to stand overnight at room temperature.Theprecipitated dyestuff of formula ylene to give greenish-tinged yellowshades.

filtered off. The filtrate is evaporated and the dyestuff of formula NU(Ella is isolated. lt dyes polyester fibres from an aqueous bath to givegreenish-tinged yellow shadesv EXAMPLE 3 29 The dyestuffs given in Table1, corresponding to the 4.4 parts of 4[N-ethyl-N-2-(4" formulamethylphenylsulphonylamidocarbonyl )oxyethylamino-2-methylbenzylidenemalodinitrile, 22.5 parts of K W methyl iodide,20 parts of potassium carbonate and 100 25 l parts by volume of methylethyl ketone are boiled for It (ll2(Tll- -U' (u as so; n about 5 hoursunder reflux. When the starting product is no longer visible in the thinlayer chromatogram, the

reaction mixture is cooled and the potassium salts are are obtained inan analogous manner.

TABLE l Continued R R R R Shade on polyesters 14 CONC21{5 -11 Cll3(heenish-tinged yellow.

l5 I ll 16 Same as above ll Clh Same as above (h'eenislrliugvd yellow.17 d II ll 0113 18 d0 I[ 011 -Cll;; (ilttlllSil-llllllfid yellow.

EXAMPLE 4 5 EXAMPLE 5 I 19.0 parts ofN-cyanethyl-NB-hydroxyethylaniline, parts of N-cyanethyl-N-2-(4'-' 20.0parts of phenylsulphonylisocyanate and 100 parts by volume of tolueneare heated for 3 hours under reflux. After cooling the product which ascrystallised out, of formula canocomrms-O (IINmethylphenylsulphonylaminocarbonyl)- oxyethylaminobenzene, 57 parts ofmethyl iodide, 50 parts of potassium carbonate and 250 parts by volumeof methyl ethyl ketone are boiled for 5 hours under reflux. The reactionmixture is then cooled and the potassium salts are filtered off. Thefiltrate is evaporated. The slightly yellowish oil is used for thecoupling reaction.

3.5 parts of sodium nitrite are dissolved in 68 parts of sulphuric acidmonohydrate. 8.15 parts of l-amino- 2-cyano-4-nitrobenzene areintroduced at to C and well stirred. After 2 hours the solution ispoured into 300 parts of ice water. The diazo solution thusobtained isadded to an acetic acid solution of 20.05 parts of the oil obtainedaccording to paragraph 1. The coupling mixture is rendered neutral toCongo Red by means of sodium acetate solution. After completion of thecoupling the precipitated dyestuff is filtered off, rinsed with waterand dried. The dyestuff of formula OHzCHaCN is filtered off, washed withwater and dried. lt dyes polyester fibres from a boiling solution inpure tetrachlorethylene (40 minutes) to give orange shades.

dyes polyester fibres in red shades having excellent fastnessproperties.

The dyestuffs of Table 2, which correspond to the formula can also bemanufactured according to the process described in Example 5.

EXAMPLE 6 0.5 parts of 50 percent strength sodium hydride dispersion areadded to a solution of 3.1' parts ofthe urethane ofN-cyanethyl-N-B-hydroxyethyl-aniline and:

phenylisocyanate (dissolved. in parts of dioxane).

After-l hour the sodium salt of the urethane had separated out as avoluminous white precipitate. Thesludge was diluted with 50 parts ofdioxane andmixedwith- 1.76 parts of benzenesulphonyl-chloride. Themixture was stirred for 2 hoursat room temperature; whereupon the whiteprecipitate disappeared and sodium.-

chloride precipitated in a fine form. Afterfilteringand working up, acolourless oil was obtained; which'correspondedto the formula CllyCl lzCN The sulphonylurethane of formula CIIzCUzCN was obtained in ananalogous-manner.

1.72 parts of 2-chloro-4-nitroaniline were diazotised.

with nitrosylsulphuric acidandthe filtered diazo solution was coupledwith 4.5 parts of the product obtained in the first paragraph (dissolvedin glacial'acetic acid: propionic acid, 5:1). The resulting. dyestuffcorresponded to the formula and dyed polyester'fibres in redshades. Thedyestuff of I formula is precipitated. by pouring-out onto ice/water.lt' dyes acetaterayon; cellulose triacetate, nylonand polyester fibresin violet shades.

EXAMPLE 8 I72 parts-of 2i-chloro-4-nitroaniline are introduced intoI83'Eparts of '1 N nitrosylsulphuric acid The diazo solutionithus.obtained is added to a solutionvof' 4-l.l parts of3-N,N-dicyano-ethylamino- N(phenylsulphonylmethylaminoearbonyl)N-methylaniline(dissolved in :500parts by volume-ofacetone). On bufferingwith sodium acetate. and'diluting the solution'with water'thedyestuff-offormula precipitates. lt dyes acetate rayon; triacetate, nylon andpolyester in red shades.

EXAMPLE 9 The dyestuff of formula N 0 2 C1 I2 ('11 i mcocm was dissolvedin hot chlorobenzene and mixed with an excess ofbenzenesulphonylisocyanate. After 3 hours stirring at 130C the solventwas evaporated off and the residue was taken up in acetone, mixed withdry potasby volume of dioxane whilst stirring at room temperature. After1 hour the sodium salt of the carbamate had separated out as a whitevoluminous precipitate. 1.72 parts of m-pyridinesulphonyl chloride wereadded whilst stirring and the mixture was stirred for 3 hours. Theprecipitated sodium chloride was filtered off. Working up of the dioxanesolution yielded a colourless viscous oil of formula was obtained, whichdyes polyester fibres in blue shades. The dyestutf of formula l l (NNIHUCHi was manufactured in an analogous manner.

EXAMPLE l0 4O 3-Amino-N,N-bis(B-acetoxyethyl)-aniline was dis- O-Nm'nuo(104,113);

was obtained. On coupling with diazotised 2-chloro-4- nitroaniline adyestuff was obtained which dyed polyester fibres in red shades.

EXAMPLE 1 1 0.5 parts of 50 percent strength sodium hydride dispersionwere added to a solution of 3.1 parts of N-cyanethyl-N,B-phenylcarbamylethylaniline in 30 parts The above productwas dissolved in glacial acetic acid and coupled with diazotisedpnitroaniline.

A red dyestuff of formula was produced. lf diazotised2-chloro-4-nitroaniline was used instead of diazotised nitroaniline, adyestuff was obtained in an analogous manner.

EXAMPLE 12 7.14 parts of 4-(N-ethyl-N,2"-cyanethyl)amino-4-sulphonamidoazobenzene are dissolved in 20 parts of dimethylformamide.2.43 parts of triethylamine and 2.86 parts of phenylisocyanate are addedand the mixture is stirred for 15 hours at room temperature. Thereafterthe reaction mixture is poured onto water, the mixture is rendered acidand the precipitated dyestuff is filtered off; the residue is washedwith water and dried.

7.3 parts of the product obtained above are dissolved in 1200 parts ofacetone and mixed with 30 parts of potassium carbonate and 30 parts ofmethyl iodide. The reaction mixture is heated for 4 hours under reflux.After cooling, the precipitated inorganic salts are filtered off and thefiltrate is evaporated. The residue is triturated with water andfiltered off.

The dyestuff of formula is obtained, which dyes polyester fibres inyellow shades of excellent fastness to sublimation.

If the dyestuff mentioned in column I is reacted with the isocyanatementioned in column II and the product is alkylated with the alkylatingagent listed in column III, dyestuffs are obtained which dye polyesterfibres in the shades mentioned in column IV.

inorganic salts are separated off by filtration and the filtrate isevaporated. The residue is then triturated with water and filtered off.The dyestuff of formula (1:1[40000111 OClls CHaN cooHi (-llul I Orange.N(

Same as above t V (113i Do.

do CHal Do.

(10 CH3I Yellow.

(3H3 (CHQzSOi Orange. Cll3-C -NCO CiHqBl Du. CH:|O NCO (CglIShSO D0.

Yollowisli red EXAMPLE 13 9.6 parts of 2,4-dinitro-b 4-(2-hydroxyethoxy)diphenylamine are dissolved in 200 parts of hotchlorobenzene. 8.25 parts of phenylsulphonylisocyanate are addeddropwise and the mixture is stirredfor a further 8 hours at 100C. Thereaction mixture is cooledand the precipitated dyestuff is filtered off,washed with chlorobenzene and dried.

is obtained, which dyes polyester fibres in yellow shades of excellentfastness to sublimation.

If the dyestuffs mentioned in column I are reacted with thesulphonylisocyanate mentioned in column [I and the resulting product isalkylated with the alkylating agent mentioned in column Ill, dyestuffsare obtained which dye polyester fibres in the shades given in columnIV.

r ii iii iv N02 01m. Yellow.

1 SO2N(J'0 (CI'ImNOCC -NIIOU;II OH 1710; Same as above Ollgl Do.chin-2N0( -C -Nu 0o2u,0u

5 parts of the product obtained above are dissolved XA 4 in 45 parts ofacetone and mixed with 20 parts of potas- 65 sium carbonate and 20 partsof methyl iodide. The reaction mixture is heated for 4 hours underreflux. The

2-(2'-hydroxyethoxy)-4-nitroaniline is diazotised and coupled toN-ethyl-N-(Z-cyanethyl)aniline. ll.5 parts of the dyestufi thus obtainedare dissolved in 75 parts of chlorobenzene. 8.25 parts ofphenylsulphonylisocyanate are added dropwise. The mixture is stirred forhours at 100C and cooled. The precipitated dyestuff is filtered off,washed with a little chlorobenzene and dried.

5.66 parts of the dyestuff condensation product obtained in paragraph 1are dissolved in 70 parts of acetone. 20 parts of potassium carbonateand 20 parts of methyl iodide are added. The reaction mixture ipolyester fibres in the shades mentioned in column V.

I II lll l\ l Cells (llxl Rod.

O2N NH: O -somco N l OCQIIlOI'I l CrlhCN 2 Same-as above t N d (jllfilltmlr NiCelhtlCUfill l ('lln --h'U;-NtU

l CH

3 do. U Cgll (llql Ollso-moo N CJILCUUCzll 4 .do Same asahovm. v. (llilOrange.

l l l l l l l (JlI3 1]. 3

o do HC(%-CH- v(lo (lllql Yellow.

no-L is (Lu. (ill dun. Ullgl li o.

ll()lI.l( 2U- -Nllg l 7 sameasabovennnvfl 011 do r r r r r (11m Orange.

8 r 110', V, V V V V V r ("lhl Em.

1{OH4C20 N 0ll NI'I2 l OOH:

heated for 4. hours under reflux. The inorganic salts are EXAMPLE thenfiltered off and the filtrate is evaporated. The residue is trituratedwith water and filtered 0h. The dyestuff of formula2-Chloro-4-nitroaniline is diazotised and coupled to1-(2'-hydroxyethyl)-3-methylpyrazolone. 9.75 parts of the dyestuff thusobtained are dissolved in parts of hot chlorobenzene. 8.25 parts ofphenylsulphonylisocyanate are added dropwise and the mixture is stirredfor a further 4 hours at lOOT. The reaction mixture is cooled, theprecipitated dyestuff is filtered off and the residue is washed withchlorobenzene and dried.

5.1 parts of the dyestuff condensation product obtained in paragraph 1are dissolved in 380parts of acetone. 20 parts of potassium carbonateand 20 parts of methyl iodide are added and the reaction mixture isheated for 3 hours under reflux. The inorganic salts are separated offby filtration and the filtrate is evaporated. The residue is trituratedwith water and filtered off. The dyestuff of formula fibres in theshades mentioned in column V are ob- EXAMPLE 16 4.57 parts of4-aminophenacyltrimethylammonium chloride are dissolved in 20 parts ofwater and 7 parts by volume of concentrated hydrochloric acid are added.The solution is diazotised at 0 to 5C by adding 5 parts by volume of 4 Nsodium nitrite solution. The diazo solution is added at 0 to 5C to asolution of 7.74 parts of N-cyanethyl-N-2(phenylsulphonyl[methylamino1carbonyl)-N,B hydroxyethylaminobenzene 30parts of acetone. After completion of coupling the dyestuff isprecipitated by adding salt. The dyestuff is filtered off, redissolvedinhot water, and salted out of the filtrate after filtering thesolution. The precipitated dyestuff'ot formula Ha is filtered off anddried. It dyes polyacrylonitnle 'l'ibres in orange shades of excellentfastness properties, I

If the amines mentioned in column I in'the table below are diazotisedand coupled as above with the coupling components mentioned in columnll, dyestuffs are obtained which dye acrylic fibres in the tained.shades mentioned in column ll]. I

I II III IV V 1.. I lI'C-C-(1ll:\ Cllal Yellow.

inoooo- -NH;- 11 -S()3NC() no -o\ /N v v l (#:llrOll 2 Sumo as nbovu. I("L'lll'i I )0.

(Jll2OOU -'N.ll2 H C- S O NC'O 3 HC-C-Clla CH3]. D0.

0:N Nl-Iz H I s OQNC o 1IOC N i N H O CzHtOH I CN HC CCH; CHaI Orange.

I II II SOzNC 0 HzN-C N O2N NHz C2H4OH I II III 9 C H CN I Scarlet. C1(CHmNomo O NH: N

CQHI'O C ONOQ S CH3 CH3 l whwwm 2 Same as above /'C2HAO 0 0 Cal-I5 Do.

C2H40COIII02S 9H1 Col-LON no. OgN N.Hz C N/ o/ OCgH N Czll- OCONOgS-Clls C1 Same as uhovu jllfq u l :iTT'Il ITTTZ H ()mmIv.

EXAMPLE 17 7.6 parts of sodium nitrite are sprinkled at to C into 90parts of concentrated sulphuric acid, the mixture is then heated at 65Cuntil everything has dissolved and is then cooled to 0C, and 100 partsby volume of a mixture of glacial acetic acid and propionic acid, in theratio of 6:1, are added dropwise. 19.4 parts of6-ethoxy-2-aminobenzthiazole, dissolved in 100 parts by volume of amixture of glacial acetic acid and propionic acid (6:1) are addeddropwise to the resulting solution and the reaction mixture is stirredfor a further 3 hours at 0 to 5C. 7.5 parts of urea are then added inportions to this diazo solution. The diazo solution thus obtained isadded, at 0 to 5C, to a solution of 38.7 parts ofN-cyanethyI-N-2(phenylsulphonyl- [methylamino]carbonyl)-oxyethylaminobenzene in 150 parts of acetone. The couplingmixture is rendered neutral to Congo Red by means of sodium acetatesolution. After completion of the coupling the solution is filtered andthe dyestuff is washed with water and dried.

8.9 parts of the dyestuff obtained above are dissolved in 150 parts ofwarm chlorobenzene. A solution of 2.85

' parts of dimenthylsulphate in parts of chlorobenzene is added dropwiseand the reaction mixture is stirred for a further 4 hours at 95 to 100C.The mixture is then cooled and filtered. The filter cake is dissolved inhot water and filtered to clarify the solution. The filtrate is saltedout. The precipitated dyestuff of formula is filtered off and dried. Itdyes polyacrylonitrile fibres in blue shades of excellent fastnessproperties.

Dyestuffs are obtained in an analogous manner if the diazo compounds ofthe amines quoted in column I are coupled with the coupling componentsmentioned in column II and the dyestuffs are treated with the alkylatingagents mentioned in column III. The dyestuffs dye acrylic fibres in theshades given in column IV.

EXAMPLE I 8 A mixture of 6.8 parts ofl-amino-4-ptoluenesulphonylamino-2-([3-hydroxyethyl)oxyanthraquinone, 6parts of p-toluenesulphonylisocyanate and 200 parts of toluene isstirred for 7 hours at room temperature and the dyestuff of formula HC20 s \S I II III IV N\ /C:II5 Dimethylsulfate Blue.

N NH II ()(UNU s (in l (1115 N (:lIrUN 110.. \iulet.

C-NIL C:IltOC.ONO;-S*C Clh S on.

IINCN]I CQHJCN do Red.

1 ll 11C N N N C2II OCONOQS- N\ Samnusahove .d0 Red. II3C do r .110Violet. --fiNH N 11 IIfil do d0 D0. 1 3CC C-NH- and dyes polyesterfibres in reddish-orange shades.

EXAMPLE 19 A mixture of 6.8 parts of l-amino-4-hydroxy-2-(B-'hydroxyethyl)oxyanthraquinone and 4 parts ofptoluenesulphonylisocyanate in 150 parts of chlorobenl 5 zene wasstirred for 7 hours at room temperature. Working up yielded 50 parts ofan orange powder which represents the dyestuff of formula 24.8 parts ofthe sulphonylurethane obtained above, 34 parts of anhydrous potassiumcarbonate, 3-1partsof dimethylsulphate and 1500 parts of acetone areboiled for hours underreflux. After working up parts-of themethylated-product were obtained as a violetpowder which corresponds tothe formula 0 NH; n l

ocmcnl 0 0 ON-S 004311 I CH:

0 I on V v and dyes polyester fibres in'bluish-tinged red shades.

EXAMPLE 20 A mixture of 12.5 parts of l-methylamino-4-aminoanthraquinone, 18 parts of benzenesulphonylisocyanate and l partofpyridine in 150 parts of toluene is boiled under reflux for 3 hours.After cooling 21 parts of a light green powder precipitate, whichcorresponds to formula h) IIlHCl-I:

W and dyes polyester fibres in violet shades.

1f 25 parts of p-toluenesulphonylisocyanate were used instead of thebenzenesulphonylisocyanate, 25 parts of a p-toluenesulphonylurea offormula (H) N HCH:

were obtained, which dyes polyester fibres in violet shades.

1f the dyestuff obtained in the first paragraph parts) was boiled with113 parts of dimethylsulphate and parts of anhydrous potassium carbonatein 1000 partsof acetone under reflux for 12 hours, a blue powderwasobtained which corresponds to the formula NllCllIl and dyespolyester'fibres in violet shades.

EXAMPLE 21 A mixture of 24 parts of l-amin0-4- 'hydroxyanthraquinone, 1part ofipyridine, 18 partsof benzenesulphonylisocyanate and 1500parts oftoluene is 'boiled for 3 hours under reflux. After cooling 40 parts of areddish-orange powder are isolated, which corresponds to the formula III 0 on and dyes polyester fibres in-orange shades.

If this dyestuff ismethylated, a valuable dyestuff ofisothiazoleanthrone, 0.5 parts of pyridine, 18 parts ofbenzenesulphonylisocyanate and 200 parts of toluene is heated for 4hours under reflux. After cooling 22 parts of a yellow powder areisolated, which corresponds'to the formula and dyes polyester fibres inyellow shades.

The compound of formula

1. A DYESTUFF OF FORMULA
 2. A dyestuff as claimed in claim 1 of theformula